Derivatives of pyrazole anthrone yellow



-- srArEs PATENT OFFICE.

EEITz smGEE AND ALFRED HOLL, 0E o EEnEAcH-omrH -MAIN, GERMANY,

\ASSIGNORS, BY- MESNE ASSIGNMENTS, TO THE CHEMICAL ronnnnrrommc A. CORPORATION 015 DELAWARE.

DERIVATIVES 0F rimXzo E ANTHEONE YEL ow.

No Drawing.

I TocZZ whom it may cancer-1b.

Be it known that' We, FRITZ SINGER and ALFRED HoLL, both citizens of the German Empire,- and residents of Oflenbach-onthe] Main, in the Grand Duchy of Hesse, Germany, have invented-new and useful In} provements in Derivatives" of? Pyrazole Anthrone Yellow; of which the following is a specification.

By melting together pyrazole lanthrone of the formula p v with caustic alkalis a'yellow vat dyestufl is I obtained, which' we' have called pyrazoleanthrone-yellow as described by German Patent 255,641. Y

.Derivatives. of thisdyestufl' are obtained by melting: together i suitable SllbStltlltlOlT products.of'pyrazoleanthrone as well asby substitution of pyra z ole 1 'anthrone yellow itself. These dyestuffs together with-p ra-. zole, anthrone-yellow itselfvw e so call'dyes of the yra'zole-anthroneyellowstype; We h cellent fastness are obtained b introducing 7 type areobtained.

However it possible to introduce but one alkyl radicals into the dyestu s of the type -'referred to hereinbefore.

i The newdyestufl's are'p roduced by treat'- ing the-alkali salts of the-dyestuff oi? the 'b pyrazole anthrone yellow {type with the esters ofacids, alkylhalids and other agents that are radicals.

The alkali salts referred tomay combine with two alkyl radicals,' whi1e the acid radical is separated by forming a salt with the metal of the alkali. 4

In this manner dialkylderivatives of-the dyestuffs of the pyrazole-anthrone-yellowave found, that new dyestuffs of ex generally used for introducing alkyl alkyliz'ing or the conditions in a suitable manner. Y a

- Thus, monoalkyl-derivatives are obtained.

for alkyl'izin'g .For example when using benz ylchlorid unreason of the der ordinary conditions by body, a'mono chemical constitution of this benzyl derivative is obtained.

' Patented Feb. 3, 1.9 1, Applicationfil ed September 23, 1915. Serial No. 52 p These monoalkyl derivatives, inopposition I to .the dialkyl derivatives,-v are capable of [forming alkali metal salts,'whichlatter may be further galkylized.

.When for this second processan agentis "used which contains-an alkyl radical difi'erent from that used in the first 5 stage of the process ,dialkyl derivatives are 'obtained,wh1ch containdiiferentalkyl 1 cals in the same molecule.

Different alkyl radicals may be introduced intomonoa-lkyl derivatives in which the alkyl group first. introduced may; not by reason of its chemical constitution ing al yl soluble in hot organic solvents e recrystallized. I v These bodies-dissolve-in an alkaline-hy drosulfite solution 'withto a bright scarlet red.

- The non substitutedf dialk'yl derivatives -are red dyestufi's', which are insoluble in tives of the "dyestufis of' the, pyrazgole-am =throne yellow-type are scarlet red dyestufl's,

which are insoluble in :water but readily.)

of a high I boiling 'point, from which solutions they may I blue colorfrom 1" which solution cotton is first dyed with blue tones, which by oxidation, become changed water aswell as in -'hot'siflverits of a high 1- boiling point; therefore by boiling the bodies"with solvents of a high boilingjpoint, i v

they can easily be 1 separated from the monoalkyl derivativesy I 9 ther introduced by using re-agents containgroup's'of lower, weight in the sec- 10n ky z -p sf 1 In this manner the ethyl and methyl radical canlbe easily introduced into the -mono- 'benzyl derivative. 'j I -The non-substitutedmonoalkyl derive 1 give with an alkaline hydrosulfite solution a blue vat,-by which cotton is d'yed in blue shades, which upon exposure to the air are While the monoalkyl derivatives, become colored black when treated with concentrated alkali metal hydroxids, whereby alkali metal salts are formed, the dialkyl derivatives are indifferent against the action of alkalis. The mixed dialkyl derivatives are scarcely distinguished from the normal dialkyl derivatives as regards their properties.

The non-substituted dialkyl derivatives changed to bordeaux-red shades of excellent fastness.

The following examples serve to illustrate the nature of our invention and in what .manner the same is to be performed. But

we wish it to be understood, that our invention is not limited to these examples nor to the proportions given therein.

Ewample 1.

sium hydro-xid until the yellow dyestufi' has been wholly transformed into the violet potassiumsalt, showing a copperlike brilliance. The solution is diluted with water until the percentage of potassium has become 3 to 5 per cent; then the salt is filtered off, and dried as thoroughly as possible by means of suction.

The thus obtained paste of the potassium salt is heated to C. during 3 hours in a. closed vessel together with l to 2 parts of 'benzylchlorid. The brown-red reaction product .is diluted with alcohol, filtered and washed with alcohol.

' The dyestufi forms a red powder and dissolves in concentrated sulfuric acid with an orange color. It is easily soluble in boiling nitrobeifzene and is precipitated therefrom when cooled as a red crystalline powder. lVhen heated with alkaline hydrosolfite a pure-blue vat is formed. Cotton is dye'd from this vat in blue tones which upon exposure to the air are changed into a very clear scarlet-red. v

*Eeam ze 2.

One part of the dyestuff obtained according to, German Patent 255,641 is heated in the form of the potassium salt, described in.

I moved. while stirring with about 1 parts of causticis much less easily soluble in nitrobenzene 6:

intensive bordeaux-red.

The alkylizing process may also be carried-out by agitating in an open vessel.- Instead of the ethyl-ester, the methyl-ester, diethyland dimethyl-sulfate etc. maybe employed. 1

Ewam-ple 3.00mplete ethg Zizz'ng of the incompletely allay Used dyestufl' obtained according to Example 2. The dyestuff obtained according to Example 2 is dissolved in 10 parts of sulfuricacid 66 1315., poured into, ice water and I washed until the acid has been fully re- The thus obtained paste is heated potash, until the mass has become deep violet black.- Aftercooling the mass is diluted with such a quantity of water, that a potassium lye of 5 to '10 per cent. is obtained and then filtered. 7

The moist alkaline residue is alkylized with the ethyl ester of p-toluene sulfonic acid, as described by Example 2. If desired the ethylizing processis repeated.

The ure diethyl derivative forms, when finely divided, a beautiful violet-red powder. which when ground shows the brilliance of brass.- It is quite fast to alkali and shows weakly basic properties. The dark-red solution of the dyestufl'in sulfuric acid becomes yel-loW-red when slowly diluted with ice, afterward pure-yellow, finally the yellow sulfate of the dyestuff is I precipitated.

By further addition of water violet-red 'E'maimple 4.Pr0ducti0n of the benzylethyl derivative.

The transformation of the monobenzyl derivative, obtained according to Example 1,

into the paste of the potassium salt and the ethylizatlon of the latter with the ethyles-ter of p-toluene sulfonic acid is performed as described in Example 3.

The product is obtained free from the unaltered monobenzyl derivative by Washing with hot nitrobenzene or by a repeated ethylization.

potash 'untiTtlie-mass has become black and v i I The properties of the product resemble in all respects the diethyl derivative def according to Example -1'are transformed scribed by Example, 3.

I v e defioaticc.

i 38 parts of the benzyl derivative obtained into the potassium salt.

The moist paste or the substance drled in cacuo is heated in an autoclave, provided with a stirrin mechanism, forfl hour to 120" C. toget er with 120 parts of the methylester of p-toluene sulfonic acid..- i

.The reaction mass diluted with .alcohol is filtered off, washed with water and dried.

The benzylmethyl-derivative forms when dried a brown red powder, which is soluble: in concentrated sulfuric acid with orange'-,

red color From the bluevat cotton is dyed posure to the air into an excellent fast red; 7 Example 6'.-P1'0vluction of 25": I

the ethyl a 44 arts of the product of ethylization obtained according to Example 2, which prod- "uct contains the-monoethyland the diethyl derivative, are heatedfor 3,- hours with 500 parts of water and 300 parts bf caustic all themonoethyl derivative has been trans formed into the potassium salt. The, obtained product is filtered oil" and the water removed by suction.

The. moist paste, orthe substance prefer- I ably dried-1'01, 'is heated for-Lhour to 120C. together with 120 parts of the methylester. of p-toluene sulfonic, acid. The further treatment corresponds to that de scribed by Example 2. c

When the product of alkylization con- .ta1ns some unaltered monoethyl derivative,

it becomes necessary to repeat the" methyl izing process-1. When completely methyl:v

ized the product forms a mixture. of the I diethyland the ethyl-methyl derivative.

The driedi's'ubstance forms :a brown-red powder, which resembles in all its properties, the diethyl derivative described by Ex- 1 J f,

. Eammp le VQ-Prbdimtibh of tie benzyl mih'o derivative...

: 91 parts of y tained by nitrating the d es'tufi' in concen trated sulfuric acid) are eatedwith sixty .,.t he foregoing. examples and forms when' parts of benzylchlorid, 3hours to 8O 85 C.' i 4 Thedyestufl is treated; as describedin 'tially as described.

the' potassium salt o f nitro derivative of pyrazole 'anthrone-yellow obwhile stirring, for

.The dyestufi' gives with alkaline 'hydro sulfitc solution a blue vat, from' which cotton dyes in blue shades, which are quickly cene dyestufl's consist ng in treating pyra zole-anthrone-yellow with alkylizin'g agents substantiallyas described.

2 --l?'rocess for the production of anthracene vdyestuffs consisting in transforming .pyrazole anthrone-yellow into monoalkyl derlvjatives by means of a partial alkylizatlon substantially as'descri-bed. e

. Now "what we claim and desire-to secure ,7

. Process' for the production of anthraas described.

1 cene dyestuffs consisting incompletely al-"' .I'kyli'z'in'g pyrazole anthrone-yellow by means qfof, the same alkylizing agent substantially in blue tones, which are changed upon ex 5:4;Pr0cess for the production of anthra monoalkylderivative and then further alradi-cal, whereby mixed dialkyl-derivatives of the said dyestufl's are obtained substan- 5. The process for the production. of an cene dyeis'tufis consistinginffir'st transform ing pyrazoleanthrone-yellow.. into the 'thracene dy'e stufi'scomprising treatingi 1 py- -ra zole anthrone'yellowwith aualkyl', alo- 'genid.

razole' anthroneyellow'with benzyl ch orid.

6. 'The process for the production of arri 7 As a new article ofmanufacture, an alkyl substituted derivative of pyraz'ole an throne yellow;

, 8. As new articles of manufacture. the

dyestuffs which are obtained by partially alkylizing '.pyrazole-anthrone yellow, which -'dyestufl'S form, when dry, 'red to brown powders,fwhich are insoluble in .water and diluted acids-soluble :in concentrated sul- .furic acid. with orange color, relatively soluble hot: nitrobenzene and other organic solvents of a high boiling point, as f. i. nitrobenzene, with orangecolor, nforming' with" alkaline 'hydrosulfite solution a blue vat;

;from which cotton dyes in blue. shades,

which in the case of non-substituted monoalkyl derivatives change into a clear yellowish red substantially as described.

9. As new articles of manufacturev the dyestuifs, which are obtained by the com.-

I plete alkylizationf of pyrazole-anthrone-yelow, containing twodifi'erent alkyl radicals,

which dyestufi's form brown red to red brown powders, insoluble in water and diluted acids, being in the absence of sulfoand hydroxylgroups indifierent-against the action of alkalis and showing weakly basic properties, the dyestuffs being soluble in concentrated sulfuric acid with dark-red color 'kylizing the latter -with a difierent 'alkyl While almost insoluble in boiling solvents of vention, We have signed our names in pres- 10 a high boiling point,- giving with alkaline ence of two Witnesses, this first day of Sephydrosulfite solution a blue vat, from which tember, 1915.

cotton dyes in blue shades, which change at H the air in the case of non-substituted clialkyl derivatives into a blue-red t0 borcleaux color of excellent fastness substantially as de- Witnesses: scribed. ANTON FEALLER,

That we claim the foregoing as our in JEAN FRICKEL. 

